Stabilization of fatty materials



Fatented Aug. 2, i 947 TEON F FATTY MATES Lox-an 0. Buxton, Newark, andCharles E. Dryden,

East Orange, N. 3., assignors to Nopco Chemical Company, Harrison, N.3., a corporation of New Jersey No Dra. Application March 27, 19%,Serial No. 528,355

15 Claims. (Cl. 167 -81) The present invention relates to thestabilization of fatty materials. More particularly, the presentinvention relates to a process for refining and stabilizing fattymaterials of marine origin containing vitamins A and D,

As pointed out in application Serial No. 375,255, filed January 21,1941, and entitled Process for refining fatty materials, now Patent No.2,345,577, vitamin-containing oils such as fish liver oils can beimproved as to physical characteristics and stabilized as to vitamins Aand D by contacting the same With vegetable meals in the presence of asolvent for the oil, and preferably a small percentage of a loweraliphatic monoc'arboxylic acid.

It has now been discovered that fatty materials of the nature of fishliver oils can be eiiectively treated with results favorably comparingwith those achieved by the practice of the aforementioned process bycontacting the fish liver oils with avegetable meal and ammonia.Preferably, there is also present an organic solvent for the oil of thesame nature as that disclosed in the aforementioned copendingapplication.

It is one of the objects of the present invention, therefore, to improvethe physical characteristics, i. e., odor, taste, etc. of fattycompounds, while at the same time stabilizing the vitamin A and Dcontent thereof, by treating such fatty compounds and/or oils with asmall percentage of ammonia.

A further object of the present invention is to contact a fatty materialof marine origin con-- taining vitamins A and D with vegetable meals inthe presence of an organic solvent for the oil, and a small percentage,for example from about 1 to 20%, of ammonia.

Still another object of the present invention is to stabilize a fattymaterial of marine origin containing vitamins A and D, as for examplefish liver oils, against oxidation by contacting the fatty material witha new antioxidant produced in situ in vegetable meals by the action ofammonia.

Other objects and advantages of the present invention will becomeapparent from the subsequent specification and specific examples.

Although in the process as practiced in accordance with applicationSerial No. 375,255 a stabilize'd form of fish liver oil or fattymaterial is produced, certain dimculties have been encountered inseparating the lower aliphatic monoc'arboxylic acid, as for exampleacetic acid, from the fish liver oil. As can be understood, the type oforganic solvent used is relatively easyto separate from the oil due toits low boiling point. A lower aliphatic monocarboxylic acid such asacetic acid has a relatively high boiling point, and the separationthereof from the fish liver oil necessarily involves heating the oil toa relatively high temperature. When ammonia is used in accordance withthe present invention, this problem is not encountered; the ammonia isvolatilized by a relatively simple and low temperature heating step. Sofar as can be ascertained, the ammonia reacts with the naturalantioxidants contained in the vegetable meals to produce newantioxidants in situ of a greatly enhanced antioxidant value and oilsolubility. Although, as previously stated, it is preferred to use asolvent for the oil in the process, it is not entirely necessary to usesuch a solvent where ammonia is used, because of the aforementionedincreased oil solubility of the new antioxidants produced in thevegetable meals. The ammonia apparently does not react with either theglyceride portion of the fish liver oils being treated or with theglyceride portion of the oils in the vegetable meal, since tests madebefore and after ammonia treatment have indicated no change in thephysical or chemical constants of the fish liver oil or of the mixtureof the meal and fish liver oil. 7

The fatty materials which may be treated in accordance with thisinvention may be any such material to which it is desired to impartincreased stability. The invention is particularly applicable to thetreatment of vitamin A or D containing materials containing one or bothof these vitamins in the alcohol or ester form. Thus, for example, fishliver oils such as cod liver oil, shark liver oil, sword fish liver oil,ling cod liver oil, tuna liver oil, halibut liver oil and the likemayall be treated, as well as vitamin concentrates prepared from such fishliver oils b saponification of the oils and extraction of theunsaponifiable fraction therefrom. Furthermore, highly potent productsprepared by high vacuum distillation of the fish liver oils may betreated with advantage; other highly potent products prepared by solventextraction of the fish liver oils or by similar methods designed toproduce a fraction having the vitamin potency concentrated therein mayalso be treated. However, othe fatty materials capable of being improvedby treatment with vegetable meals may also be processed; for example,this invention may be applied to the refining of cottonseed oil, soybeanoil; peanut oil, sesame oil, lard and similar products.

Any vegetable meal may be employed in the practice of this invention,particularly those rich in natural antioxidants; thus, for example,cottonseed meal, soybean meal, sesame meal, corn meal, corn germ meal,wheat germ meal, alfalfa leaf meal, peanut meal, rice bran, rye, barley,and other vegetable meals known to the art may be employed. These mealsmay be prepared by either cold pressing or expelling oil from thevegetable and grinding, or by extracting the oil from the vegetable witha solvent and grinding. Preferably, however, a meal having a low oilcontent prepared by cold pressing or expelling oil from the vegetablemeal is employed. If desired, an adsorbent, such as activated carbon oran activated earth, may be added to the meal in order to assist in theremoval of the objectionable odor, taste and color-forming constituents.It is advantageous to substantially completely deaerate the meal beforeit is employed in the practice of my invention in order to minimizeoxidation of the vitamins during the refining process; this deaerationmay be advantageously carried out by agitating the meal with the solventto be employed until the entrapped air has been driven fro-m the meal.

The solvent employed in the practice of this invention should be one inwhich the fatty material to be refined is readily soluble. Thus if afish liver oil or concentrate prepared therefrom is being treated, ahydrocarbon or halogenated hydrocarbon solvent such as hexane, heptane,octane, ethylene dichloride, trichlorethylene, carbon tetrachloride,cyolohexane, methyl cyclohexane or benzene may be employed as thesolvent, as well as solvents such as acetone, isopropanol, diacetonealcohol and the like. In some instances mixtures of the aforementionedsolvents may be found desirable for use in the process.

Preferably, the present process is carried out by mixing a vitamin A orD containing material of the characteristic set forth with a solventmixture, a vegetable meal and a small quantity of concentrated aqueousammonium hydroxide and then refluxing the mass in an inert atmospherefor a short period in order to release the antioxidants produced in themeal by the ammonia.

However, in the event that ammonia gas is used,

the process may be carried out in an open vessel equipped with a refluxcondenser or in a closed vessel under'pressure of the ammonia gas. Inthis instance, also, the process may be carried out in the absence of anorganic solvent. eral, however, the presence of an organic solvent ofthe character described is preferred, since lower temperatures andshorter times of treatment can be used and better results obtained.

The amount of ammonia used is relatively small as compared to thequantity of fatty material and vegetable meal and may vary from about 1to by weight of concentrated aqueous ammonia, as compared to the weightof the fatty material, i. e. fish liver oil and the like. When gaseousammonia or liquid ammonia is used, the amount is equivalent to that justset forth. The amount of vegetable meal may vary substantially but. ingeneral, it is desirable to employ between In gen about 5 parts to partsor more by weight of meal to 100 parts of fatty material. The amount ofsolvent employed should be at least equivalent to, and preferablysomewhat in excess of, the amount of material being refined The processmay be carried out at room temperature, or ele vated temperatures may beemployed. After the mixture has been thoroughly agitated for betweenabout /2 and about 3 hours, the meal may be removed by filtration andthe refined material recovered by evaporation of the solvent.

The following examples serve to illustrate the present invention but arenot intended to limit the same.

Example I A mixture of 30 grams of carbon-refined shark liver oilcontaining 57,300 units of vitamin A per gram, 30 grams ofexpellenlinseed meal, ml. of acetone and 10 ml. of concentrated ammoniumhydroxide were mixed andheated at reflux temperature for 2 hours.Thereafter, the mixture was cooled to room temperature, filtered and thesolvent evaporated. The resultant product contained about 53,000 vitaminA units per gram and was improved in taste and odor. The product wasthen tested for its stability by maintaining it at a temperature ofapproximately 34.5 C. in the presence of air with the following results:

Per Cent Vilmnin A Destroyed Afler- Sample I 6 days Ill days days 1 mo.3 mos.

Product of Example I... 0 2. G5 1.13 5. 3 9. 42 Original Oil l8. 5 52. 0

Example II A similar carbon-refined shark li er oil containing 56.500units of vitamin A per gram was similarly treated with quantities ofexpeller linseed meal, acetone, and concentrated ammonium hydroxide asset forth in Example I. The following results were obtained.

Per Cent Vitamin A Destroyed Altor Sample 6 days 14 days 20 days 1 mo. 3mos.

Product of Example II (48,800 units A/gr.) 0 3. 28 2. G0 6.15 9. 4Original Oil 27 62.5

Example III Per Cent Vitamin A Destroyed After- Sample 6 days 14 days 20days 27 days 2 mos.

Product of Example III (52,000 units A/gr.) 0.385 2. 77 3.08 5. 2 9. 24Original Oil 27 62. 5

Example IV Thirty grams of a carbon-refined shark liver oil containing56,500 units of vitamin A per gram Per Cent Vitamin A Destroyed Af er-Sample Gdeys l4days 20days 31 days Product of Example IV (49,200

units A/gr.) l. 02 0. 47 3. 5 Original Oil 27 62. 5

Example V Thirty grams of a carbon-refined shark liver oil and 30 gramsof expeller linseed meal were thoroughly admixed and thereafter ml. ofconcentrated ammonia were added. The entire mass was then agitatedintermittently over a period of 2 hours. Thereafter the mass was heatedslowly while subjected to a stream of nitrogen to ex- Del the ammonia.The oil was then separated from the meal bydissolving the same in asmall amount of acetone and filtering. The resultant product wassubstantially improved in stability.

It will be noted from the above examples that the fish liver oilstreated have been greatly improved as to vitamin A stability. Similarresults can be obtained by utilizing other solvents of the characterpreviously set forth and ammonia in other forms. It is desired to pointout, therefore, that when in the appended claims the term amm0nia-isused, liquid or gaseous ammonia, and ammonia dissolved in water or othersuitable solvent therefor is intended.

Having described our invention, What we claim as new and desire tosecure by Letters Patent is:

1. A process for stabilizing a fatty material comprising contacting thefatty material with a vegetable meal in the presence of a relativelysmall amount of ammonia.

2. A process for stabilizing a vitamin-containing fatty material ofmarine origin comprising contacting said fatty material with a vegetablemeal in the presence of a relatively small amount of ammonia.

3. A process for stabilizing a. fatty material comprising contactingsaid fatty material with a vegetable meal in the presence of arelatively small amount of ammonia and heating the meal, fatty materialand ammonia.

4. A process for stabilizing a fatty material comprising contacting saidfatty material with a vegetable meal in the presence of a solvent forthe fatty material and a relatively small amount of ammonia.

5. A process for stabilizing a vitamin-containing fatty material ofmarine origin comprising contacting said fatty material with a vegetablemeal in the presence of a solvent or the fatty material and a"relatively small amount of ammonia.

6. A process for stabilizing a vitamin-containing fatty material ofmarine origin comprising essence contacting said fatty material with avegetable meal in the presence of a solvent for the fatty material andfrom about 1 to 20% of ammonia.

'Z. A process for stabilizing a fish liver 011 comprising contacting thefish liver oil with a vegetable meal in the presence of a relativelysmall amount of ammonia.

8. A process for stabilizing a fish liver oil comprising contacting saidfish liver oil with a vege-.

table meal in the presence of a solvent for the fish liver oil and fromabout 1 to 20% of ammonia.

9. A process for stabilizing a fish liver oil comprising contacting saidfish liver oil with a vegetable meal in the presence of acetone and fromabout 1 to 20% of ammonia.

10. A process for refining a fish liver 011 comprising contacting saidfish liver oil with a vegetablemeal in the presence of. acetone and from1 to 20% of a concentrated aqueous solution of ammonia.

11. A process for stabilizing a fatty material comprising contactingsaid fatty material with a vegetable meal in the presence of a solventfor the fatty material and a relatively small amount of ammonia andthereafter refluxing the fatty material, meal, solvent, and ammoniamixture.

12. A process for stabilizing a vitamin-containing fatty material ofmarine origin comprising contacting said fatty material with a vegetablemeal in the presence of a solvent for the fatty material and arelatively small amount of ammonia, refluxing the mixture of fattymaterial, meal, solvent, and ammonia, separating the meal from the fattymaterial and solvent and thereafter removing the solvent and excessammonia.

13. A process for stabilizing a vitamin-containing fatty material ofmarine origin comprising contacting said fatty material with a vegetablemeal in the presence of acetone and a relatively small amount ofammonia, refluxing the mixture of fatty material, meal, acetone, andammonia, separating the meal from the fatty material and acetone andthereafter removing the acetone and excess ammonia.

14. A stabilized vitamin-containing fatty material of marine originobtained by the process defined in claim 12.

15. A stabilized vitamin-containing fatty material of marine originobtained by the process defined in claim 13.

LORAN O. BUXTON. CHARLES E. DRYDEN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,345,577 Buxton Apr. 4, 1944OTHER REFERENCES Pharmaceutical Abstracts of the Journal of the AmericanPharmaceutical Association, vol. 1, page 116 (1935).

